Azo dyestuffs



Patented June 22, 1937 PATENT OFFICE AZO DYESTUFFS Joseph Gyr and Otto Kaiser, Basel, Switzerland,

assignors to Society of Chemical Industry in Basie, Basel, Switzerland No Drawing. Application July 26, 1935, Serial No. 33,416. In Switzerland July 30, 1934 9 Claims.

It has been found that new dyestuffs capable of being coppered on the fiber or in substance can be obtained by coupling a diazo-compound of the general formula 1 in which R1 represents the radical of a compound of the benzene series which is characterized by the presence of an OH-group and a COOH-group in ortho-position to each other, with a coupling component of the general formula HOaS in which y stands for a radical wherein R2 represents the radical of a compound of the benzene series characterized by the presence of an OI-I-group and a COOH-group in ortho-position to each other, and 2 represents a hydrogen atom or any desired monovalent radical linked to the carbon atom by an S, O or N-bridge, and in which :1: stands for a hydrogen atom or an SOaH-group, in which further the sulfo-group m can only stand in the 3- or -position to the r p 1 standing in the 1-position.

As compounds of the benzene series represented by the radicals R1 and R2, which are characterized by the presence of an OI-I-group and a COOH- group in ortho-position to each other, there may be cited inter alia the para-aminosalicylic acid, the ortho-aminosalicylic acid, the para-aminoortho-cresotihic acid, the 4-su1fo-6-amino-l-hydroxybenzene-2-carboxylic acid, the 4-aminoor 3' amino 4 hydroxyazobenzene- 3 -carboxylic acid, the 4-amino-4-hydroxy-3-methylazobenzene-5-carboxy1ic acid, the 4- or 3-aminobenzoyl-amino-salicylic acid, the 4-amino4-hydroxydiphenylamino-2-sulfo3-carboxy1ic acid, the azimide-like or imidazole-like products which are obtained for example by condensing dinitrochlorbenzene and 4-amino-salicy1ic acid, reducing and diazotizing the condensation product, and so forth. The alkyl-group of the O-alkyl radical of the diazotizing component may consist of 1 or 2 carbon atoms, it may also be of high molecular weight, or of a more complicated composition, such as an OCHs-group, an OCzHsgroup, an OCHz-CHz-OH-group, an OCHz-CI-Iz- O-CHa-group, an O-CHz-COOCzHs-gmup, an O-CI-Iz-CQONH-alkyl-group, an O-CH2-CH2- CH3gr0up, an O-cHz-Cl-lz-cHz-CHs-group, an

and the like.

The coupling components which correspond to the above explained formula are obtained quite generally by causing 1 mole of cyanuric chloride to react with an aminohydroxynaphthalene-sulfonic acid, such as the l-amino-B- hydroxynaphthalene-3:6-disu1fonic acid, the 1- amino-8-hydroxynaphthalene-4 fi-disulfonic acid the 1-amino-8-hydroxynaphthalene-6-sulfonic acid, the 1-amino-5-hydroxynaphtha1ene-7-su1- ionic acid, the 2-amino-5-hydroxynaphthalene-7- sulphonic acid or the 2-amino-8-hydroxynaphthalene-S-sulfonic acid, and by causing 1 mole of one of the above defined compounds of the benzene series to react with 1 mole of the condensation product thus obtained. The secondary condensation products thus formed may be used as such, they may also be united with the diazo compound only after the last labile chlorine atom of the cyanuric chloride has been exchanged for any desired radical which may be, inter alia, the radical 01 water, of ammonia, of monomethylamine, of dimethylamine, of aniline, of toluidine, of monomethylaniline, of ethyl alcohol, of phenol, of thiophenol, of ethers of aminophenol, or of the above characterized compounds of the benzene series or of the cited aminonaphthols. In

the latter case there are obtained azo-dyestuffs of high molecular weight, since there may be used 2 moles of diazo compound.

Consequently, the new dyestuffs correspond to the general formula (l)alkyl OH wherein R2 represents the radical of a compound of the benzene series which is characterized by the presence of an OH- and a COOH-group in orthoposition to each other, and 2 represents an IzI-atcin ora monovalent radical linked to the carbon atom by an S- or N-briolge, :0 stands for a hydrogen atom or a SOaI-I-group, in which formula further the sulfo-group a: can only stand in the 3- or OOHa OH standing in l-position, and in which 1; stands for hydrogen or an SOsH-group. The new products are dark powders which dissolve in water on addition of alkalies to blue to green solutions and dye cotton from a neutral or weakly alkaline bath similar tints which, when after-treated with copper on the fiber, become fast to light and Washing. The dyeings produced with these dyestufis have the advantage of better fastness to washing as compared with the dyeings of the dyestuffs containing the cyanuric ring of Patents 1,667,312 and 1,808,849 which also contain an OI-I-group and a COOH-group in ortho-position to each other. The new dyestufis may also be used in the form of their copper compounds. They may further be used for dyeing regenerated cellulose, such as viscose artificial silk.

The following example illustrates the in- Vention:

The diazo-compound made in the known manner from 417 parts by weight of the aminoazodyestufi from diazotized 4-amino-1-hydroxybenzene-Z-carboxylic acid and l-amino-2-methoxynaphthalene-6-sulfonic acid is coupled, at 0-5 C., in presence of pyridine, with 664 parts of the ternary condensation product from 1 mol. cyanuric chloride, 1 mol. of 2-amino-5-hyclroxynaphthalene-'l-sulfonic acid, 1 mol. l-amino-4- hydroxyazobenzenee3'-carboXylic acid and 1 mol. aniline. There is obtained a pure green fast to light. The dyeing on cotton, after treated with copper sulfate, is characterized by excellent fastness to washing and good fastness to light. The new dyestuff has the following formula COOH COOH N if the 2-amino-5-hydroxynaphthalene-'l-sulfonic acid is exchanged for 1-amin0-8-hydroxynaphthalenelzG-disulfonic acid there is obtained a yelloWish-green-dyeing dyestufi of the formula.

The formula of dyestuff No. 14 of the foregoing table is OCH; OH

SOHH S 03H In the following table there 15 set forth a number of dyestuffs WhlCh are obtamableby thepresent 1nvent1on:

- Color of dyeing on Starting component Middle component Condensatlon g gga iggfi fig gi chloride with cotton subsep quently coppered (1) 4-amino-l-hydroxybenzene- 1-amino-2-meth0xl-amino-8-hydrox- 4 (4 aminoben- 4 (4 aminoben- Green.

2-carboxylic acid. ynaphthalene ynaphthalene zoyl) amino lzoy1)-amino 1 6 -sulfonic acid 3:6 disulfonic hydroxybenhydroxybenacid. zene 2 carb0xzene 2 carb0xylic acid. ylic acid. (2) do do 2-amino-5-hydroxdo do Greenish blue. ynaphthalene 7 sulfonic acid. (3) do do do 4-amino-4hydrox- Green.

yazobenzene 3 carboxylic acid. (4) -.-.d0 do do 4- amino-5-1neth- 4" amino- 6-meth- Green.

oxy 2 methoxy 2' methyl 4- hydroxy yl -4 hydroxyazobenzene 3 azobenzene 3 c a r b o x y 1i 0 carboxylic acid. acid. I (5) do. (2 mol.) do. (2 mol d0 2-amino-5-hydr0xdo Green.

ynapbthalene 7 carboxylic acid. (6) 4-amino-4-hydroxyazoben- 1-amino-2-Inethox- 1-amino-8-hydrox- 4-a1nino-4-l1ydr0x- 4-amino-4-hydrox- Pure olive-green.

zene 3 carboxylic acid. ynaphthalene ynaphthalene ya z o b e n z e n eyazobenzene 3- G-sulionic acid. 3:6 disulfonic 3 carboxylic carboxylic acid.

acid. acid. (7) 4-amin0-l-hydroxybenzene- ...do do do do Yellow green.

-' Z-carboxylic acid. (8) 'i-amino-4-hydroxyaz0bendo l-amino-B-hydroxdo Aniline Green.

Zena-3 carboxylic acid. ynaphthalenc 4 z 6 disnlionic acid.

(9) 4-amino-l-hydroxybenzened0 do 4-a1nino-1-bydrox- Green blue.

Z-carboxylic acid. ybenzene 2 carboxylic acid. (10) 4-amino-1-hydroxybenzene 1-a1nino-2-methl-amino-S-hydroxy- 4(4-a1ninoben- 4(4-aminoben- Greenish blue.

2-carboxylic acid. oxynaphthalene naphthalene-4: 6- zoyl) amino 1 zoyl) amino 1 fi-sulionic acid. disulfonic hydroxybenhydroxybenacid. zene 2 carbox zene 2 carbox ylic acid. ylic acid. (11) do do 1-an1ino-8-hydroxydo do Blue green.

naphthalene-3: 6- d i s u l f o n i c acid. (12) do do do 4-amino-1-hydroxy- Green blue.

benzene 2 car boxylic acid. (13) rln do do do 4-amino-1-hydroxy- Green blue.

benzene 2 car boxylic acid. (14) 6-amin0-1-hydroxybenzene- .do do 4-an1ino-4-hy- Aniline Yellowish green.

2-carboxylic acid. droxyazoben zene 3 carbox ylic acid. (15) 4-amino-l-hyd1-oxybenzened0 2-amino-8-hydr0xy- 4-amino-l-hydroxy- 4-amino-l-hydroxy- Greenish blue.

2-carboxy1ic acid. naphthalene-G- benzene-Z-carbenzene-2-carsulfonic acid. boxylic acid. boxylic acid. (16) do l-amino-fi-hydroxydo do Green blue.

naphthalene-7- sulionic acid.

The formula of dyestuff No. 2 of the zoregomg C O O H table is S 0 311 N/ N C O O H H l 0 CH3 NE-C CNHOC ONH- OH (EOOH The formula of d'yestuff No. 16 of the foregoing table is other e for a hydrogen atom, one y stands for hydrogen and the other y for the radical H033 NIH-O N V l \NC%NH on OCHa 00011 0HQN=N- N=N OOOH H When the dyestuffs are dyed in the form of their copper compounds similar tints are obtained. What we claim is:- 1. The azo-dyestuffs of the formula a -N-c N olk 0 I :1 Y1 H 1/ Q M I Z (in which R1 is a member of the group consisting c0011 ofmonocyclic aryl radicals characterized by hav- SOaH ing an OH- and a COOK-group in ortho-position in which one 2 stands for an OH-group and the other .2 for a hydrogen atom, 2; stands for a member of the group consisting of hydrogen and the SO3I-I-group, one y stands for hydrogen and the other 1 for the radical (in which R1 is a member of the group consisting of monocyclic aryl radicals characterized by having an OI-I- and a COOH-group in ortho-position to each other, and radicals of the formula A-B-C, where A is a monocyclic aryl radical, B is a member of the group consisting of Q N H l 0 H and N=N-, and C is a monocyclic aryl radical having an OH- and a COOH-group in orthoposition to each other, and R2 stands for a radical of a monocyclic aryl amine), and in which formula the two :cs stand for hydrogen if the y standing in a-position represents a hydrogen atom, and one of the zrs stands for hydrogen and the other :0 for an SOzH-gl'oup if the y standing in fl-position represents a hydrogen atom, which products are dark powders dissolving in water on addition of alkalies to blue to green solutions and dyeing cotton from a neutral or weakly alkaline bath similar tints which, when after-treated with copper on the fiber, become fast to light and washing.

2. The azo-dyestufi's of the formula ([)alkyl (iJH y z N=N N=N 1 z 1 OOH in which one 2 stands for an OH-group and the to each other, and radicals of the formula -ABC, Where A is a monocyclic aryl radical, B is a member of the group consisting of and N=N-, and C is a monocyclic aryl radical having an OH- and a COOH-group in ortho-position to each other, and R2 stands for a radical of a monocyclic aryl amine), and in which formmula the two ats stand for hydrogen if the 11 standing in oc-IIJOSitlOIl represents a hydrogen atom, and one of the arts stands for hydrogen and the other :I: for an SOsH-group if the 21 standing in c-position represents a hydrogen atom, which products are dark powders dissolving in water on addition of alkalies to blue to green solutions and dyeing cotton from a neutral or weakly alkaline bath similar tints which, when after-treated" with copper on the fiber, become fast to light and washing.

3. The azo-dyestufis of the formula O-alkyl OH z N=N N=N y Z 7-1 COOH S0311 SOsH in which one 2 stands for an OH-group and the other 2 for a hydrogen atom, one y stands for hydrogen and the other-" for the radical (in which R1 is a member of the group consisting of monocyclic aryl radicals characterized by having an OI-I- and a COOI-I-group in ortho-position to each other, and radicals of the formula which product is a dark powder dissolving in water on addition of alkalies to green solutions and dyeing cotton from a neutral or weakly alkaline bath similar tints which when after-treated with copper become green and fast to light and washing.

6. The azo-dyestuffs of the general formula --AB-C, where Ais a monocyclic aryl radical, B is a member of the group consisting of and -N=N, and C is a monocyclic aryl radical having an OH- .and a COOH-group in ortho- H N-O J) 1 OOH Oalkyl OH N-o N HO N= N= 303B som position to each other, and R2 stands for the radical of aniline), and in which formula the two ms stand for hydrogen if the y standing in zposition represents a hydrogen atom, and one of the xs stands for hydrogen and the other a: for an SO3H group if the 11 standing in fl-position represents a hydrogen atom, which products are dark powders dissolving in water on addition of COOH alkalies to blue to green solutions and dyeing cotton from a neutral or weakly alkaline bath similar tints which, when after-treated with copper on the fiber, become fast to light and washing.

in which one a: stands for a hydrogen atom, the otherccstands for an SOaH-group and alkyl stands for a member of the group consisting of CH3 and C2H5, which roducts are dark owders dissol 4. The azo-dyestufis of the general formula p p V 0-alkyl OH O Q' I NC 0 OH SOaH in which alkyl stands for a member of the group consisting of CH3 and C2H5, which products are dark powders dissolving in water on addition of alkalies to green solutions and dyeing cotton from a neutral or weakly alkaline bath similar tints, which, when after-treated with copper, become green and fast to light and washing.

5. The azo-dyestuff of the formula ing in water on addition of alkalies to green solutions and dyeing cotton from a neutral or weakly alkaline bath similar tints which, when aftertreated with copper, become green and fast to light and washing.

SOaH

8. The azo-dyestuff of the formula which product is a dark powder dissolving in wafil I g V 0on5 OH NHC C-NHGN: OOH I OH N: N=N 10 coon 303K 503B SOaH which product is a dark powder dissolving in water on addition of alkalies to green solutions and dyeing cotton from a neutral or weakly alkaline bath similar tints which, when after-treated with copper, become green and fast to light and washing.

ter on addition of alkalies to green solutions and dyeing cotton from a neutral or weakly alkaline bath similar tints which, when after-treated with copper, become green and fast to light and washmg.

9. The azo-dyestuff of the formula c0011 f r OOH; OH NH-O cam-QM: 00H I \N OHQN= N=N 00011 SOaH JOSEPH GYR.

sc n SOs-H or'ro KAISER. 

